Resin composition and shaped product

ABSTRACT

Provided are a resin composition and a shaped product having excellent smoke generation properties and chemical resistance. The resin composition and the shaped product contain: a polyphenylene ether resin (I); a polypropylene resin (II); a hydrogenated block copolymer (III) that is a hydrogenated product of a block copolymer including a polymer block A and a polymer block B in which the total amount of vinyl bonding is 30-90%; and a phosphate ester compound (IV). Relative to 100 parts by mass, in total, of components (I) and (II), component (I) is 40-99 parts by mass, component (II) is 1-60 parts by mass, component (III) is 1-20 parts by mass, and component (IV) is 5-45 parts by mass. A partition ratio of component (IV) present in a fraction that dissolves in chloroform and component (IV) present in a fraction that dissolves in o-dichlorobenzene is 10 or more.

TECHNICAL FIELD

This disclosure relates to a resin composition and a shaped product.

BACKGROUND

Although polypropylene has excellent shaping processability, waterresistance, oil resistance, acid resistance, alkali resistance, and soforth, it is also known to have poor heat resistance and rigidity.Accordingly, a known technique of compounding polyphenylene ether withpolypropylene may be adopted to obtain a resin composition havingenhanced properties in terms of heat resistance, rigidity, and so forth.

Examples of techniques for further imparting flame retardance on thisresin composition include a commonly adopted technique of adding ahalogen-containing compound and antimony trioxide. However, since flameretardants such as halogen-containing compounds and antimony trioxideare undesirable from a viewpoint of environmental health, there isdemand for improved flame retardance imparting techniques, such astechniques using flame retardants that do not contain halogen-containingcompounds, antimony trioxide, or the like.

Examples of known techniques for responding to this demand include atechnique of compounding a flame retardant such as a metal salt ofphosphinic acid with a polyphenylene ether resin and a polypropyleneresin (for example, refer to PTL 1 to 3). Moreover, PTL 4 and 5 disclosethe use of another flame retardant or flame retardant synergist inaddition to a metal salt of phosphinic acid to obtain a resincomposition having even better flame retardance.

CITATION LIST Patent Literature

PTL 1: JP 2010-540716 A

PTL 2: WO 2011/129129 A1

PTL 3: JP 2013-14691 A

PTL 4: JP 2014-159513 A

PTL 5: JP 2014-210839 A

SUMMARY Technical Problem

However, although flame retardance can be obtained in the resincompositions described in the aforementioned patent literature, thechemical resistance that is characteristic of a resin compositioncontaining a polyphenylene ether resin and a polypropylene resin may belost. In particular, it has been reported that in a case in which aliquid organophosphate is also used in such a resin composition asdescribed in PTL 4 and 5, stability of morphology of the resincomposition is lost, resistance to machine oil and mold cleaning agentsis reduced, and the resin composition may be affected by such chemicalsduring shaping processing, leading to cracking. Moreover, these resincompositions suffer from a problem that, in a case in which the contentof the polyphenylene ether resin is increased in order to increase flameretardance and shaping fluidity, the density of smoke generated duringburning increases and smoke generation properties are negativelyaffected.

Accordingly, an objective of this disclosure is to provide a resincomposition and a shaped product having excellent smoke generationproperties and chemical resistance.

Solution to Problem

As a result of diligent investigation conducted to solve the problemsset forth above, the inventors discovered that these problems can bebeneficially solved through a resin composition and a shaped productthat contain a polyphenylene ether resin, a polypropylene resin, ahydrogenated block copolymer having a specific structure, and aphosphate ester compound as a flame retardant in specific proportions,and particularly in which a partition ratio of phosphate ester compoundpresent in a fraction that dissolves in chloroform and phosphate estercompound present in a fraction that dissolves in o-dichlorobenzene iswithin a specific range. The inventors completed the present disclosurebased on these discoveries.

Specifically, this disclose provides the following.

[1] A resin composition comprising:

a polyphenylene ether resin (I):

a polypropylene resin (II):

a hydrogenated block copolymer (III) that is an at least partiallyhydrogenated product of a block copolymer including a polymer block A ofmainly a vinyl aromatic compound and a polymer block B of mainly aconjugated diene compound in which a total amount of 1,2-vinyl bondingand 3,4-vinyl bonding is 30% to 90%; and

a phosphate ester compound (IV), wherein

relative to 100 parts by mass, in total, of the polyphenylene etherresin (I) and the polypropylene resin (II):

the polyphenylene ether resin (I) is contained in an amount of 40 partsby mass to 99 parts by mass:

the polypropylene resin (II) is contained in an amount of 1 part by massto 60 parts by mass;

the hydrogenated block copolymer (III) is contained in an amount of 1part by mass to 20 parts by mass; and

the phosphate ester compound (IV) is contained in an amount of 5 partsby mass to 45 parts by mass, and

upon dissolution of the resin composition in chloroform, a ratio(IV)_((I))/(IV)_((II)) is 10 or more, where (IV)_((I)) representscontent of the phosphate ester compound (IV) present in a fraction thatdissolves in chloroform and (IV)_((II)) represents content of thephosphate ester compound (IV) present in a fraction that dissolves ino-dichlorobenzene.

[2] The resin composition according to the foregoing [1], wherein

the ratio (IV)_((I))/(IV)_((II)) is 250 or less.

[3] The resin composition according to the foregoing [1], wherein

the ratio (IV)_((I))/(IV)_((II)) is 199 or less.

[4] The resin composition according to any one of the foregoing [1] to[3], wherein

the ratio (IV)_((I))/(IV)_((II)) is 15 to 199.

[5] The resin composition according to any one of the foregoing [1] to[4], further comprising

3 parts by mass to 15 parts by mass of at least one phosphinate salt (V)selected from the group consisting of:

a phosphinate salt represented by formula (1)

where R¹¹ and R¹² are each, independently of one another, a linear orbranched alkyl group having a carbon number of 1 to 6 and/or an arylgroup having a carbon number of 6 to 10, M¹ is at least one selectedfrom the group consisting of a calcium ion, a magnesium ion, an aluminumion, a zinc ion, a bismuth ion, a manganese ion, a sodium ion, apotassium ion, and a protonated nitrogenous base, a is an integer of 1to 3, m is an integer of 1 to 3, and a=m; and

a diphosphinate salt represented by formula (2)

where R²¹ and R²² are each, independently of one another, a linear orbranched alkyl group having a carbon number of 1 to 6 and/or an arylgroup having a carbon number of 6 to 10, R²³ is a linear or branchedalkylene group having a carbon number of 1 to 10, an arylene grouphaving a carbon number of 6 to 10, an alkylarylene group having a carbonnumber of 6 to 10, or an arylalkylene group having a carbon number of 6to 10. M² is at least one selected from the group consisting of acalcium ion, a magnesium ion, an aluminum ion, a zinc ion, a bismuthion, a manganese ion, a sodium ion, a potassium ion, and a protonatednitrogenous base, b is an integer of 1 to 3, n is an integer of 1 to 3,j is an integer of 1 or 2, and b-j=2n.

[6] The resin composition according to any one of the foregoing [1] to[5], wherein

the total amount of 1,2-vinyl bonding and 3,4-vinyl bonding in theconjugated diene compound of the polymer block B is 65% to 90%, and

the conjugated diene compound of the polymer block B includes butadiene.

[7] The resin composition according to any one of the foregoing [1] to[6], wherein

the phosphate ester compound (IV) includes a condensed phosphate ester.

[8] The resin composition according to any one of the foregoing [1] to[7], wherein

the resin composition has a morphology in which a phase containing thepolyphenylene ether resin (I) and a phase containing the polypropyleneresin (II) are co-continuous or a morphology in which a phase containingthe polypropylene resin (II) is a matrix.

[9] A shaped product comprising the resin composition according to anyone of the foregoing [1] to [8].

Advantageous Effect

According to this disclosure, it is possible to provide a resincomposition and a shaped product having excellent smoke generationproperties and chemical resistance.

BRIEF DESCRIPTION OF THE DRAWING

In the accompanying drawing,

FIG. 1 provides an overview of Production Methods 1 to 7 used inproduction of resin compositions in examples and comparative examples ofthis disclosure.

DETAILED DESCRIPTION

The following provides a detailed description of an embodiment of thisdisclosure (hereinafter, referred to as the “present embodiment”).However, this disclosure is not limited to the following embodiment andmay be implemented with various alterations that are within theessential scope thereof.

(Resin Composition)

A resin composition of the present embodiment contains a polyphenyleneether resin (I), a polypropylene resin (II), hydrogenated blockcopolymer (III), and a phosphate ester compound (IV), and may optionallycontain a phosphinate salt (V), a thermoplastic resin (VI) other thancomponents (I) and (II), and an additive (VII) other than components (I)to (VI).

The following describes the components in the resin composition of thepresent embodiment.

The resin composition of the present embodiment has excellent smokegeneration properties with the density of smoke generated during burningbeing low, and has excellent chemical resistance with the tensilestrength retention rate after chemical immersion being high.

Moreover, a preferred resin composition of the present embodiment hasexcellent flame retardance. In the present embodiment, excellent flameretardance is defined as a flame retardance level of V-1 or higher in aUL94 vertical burning test.

—Polyphenylene Ether Resin (I)—

The polyphenylene ether resin (I) used in the present embodiment may be,but is not specifically limited to, a polyphenylene ether, a modifiedpolyphenylene ether, or a mixture of both. Component (I) may be one typeused individually, or two or more types used in combination.

From a viewpoint of further improving flame retardance of the resincomposition, the reduced viscosity of component (I) is preferably 0.25dL/g or more, and more preferably 0.28 dL/g or more, and is preferably0.45 dL/g or less, more preferably 0.36 dL/g or less, and particularlypreferably 0.35 dL/g or less. The reduced viscosity can be controlledthrough the polymerization time and the amount of catalyst.

The reduced viscosity can be measured as ηsp/c of a 0.5 g/dL chloroformsolution at a temperature of 30° C. Specifically, the reduced viscositycan be measured by a method described in the subsequent EXAMPLESsection.

—Polyphenylene Ether—

The polyphenylene ether may be, but is not specifically limited to, ahomopolymer formed from a repeating unit structure represented by thefollowing formula (3) or a copolymer including a repeating unitstructure represented by the following formula (3).

[In formula (3), R³¹, R³², R³³, and R³⁴ are each, independently of oneanother, a monovalent group selected from the group consisting of ahydrogen atom, a halogen atom, a primary alkyl group having a carbonnumber of 1 to 7, a secondary alkyl group having a carbon number of 1 to7, a phenyl group, a haloalkyl group, an aminoalkyl group, anoxyhydrocarbon group, and an oxyhalohydrocarbon group in which a halogenatom and an oxygen atom are separated by at least two carbon atoms.]

Commonly known examples can be used as the polyphenylene ether withoutany specific limitations. Specific examples of polyphenylene ethers thatcan be used include homopolymers such as poly(2,6-dimethyl-1,4-phenyleneether), poly(2-methyl-6-ethyl-1,4-phenylene ether),poly(2-methyl-6-phenyl-1,4-phenylene ether), andpoly(2,6-dichloro-1,4-phenylene ether); and copolymers such ascopolymerized products of 2,6-dimethylphenol with another phenol such as2,3,6-trimethylphenol or 2-methyl-6-butylphenol.Poly(2,6-dimethyl-1,4-phenylene ether) and a copolymer of2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, andpoly(2,6-dimethyl-1,4-phenylene ether) is more preferable.

The method by which the polyphenylene ether is produced is notspecifically limited and may be a conventional and commonly knownmethod. Specific examples of polyphenylene ether production methods thatcan be used include a method described in U.S. Pat. No. 3,306,874 A inwhich a polyphenylene ether is produced through oxidative polymerizationof 2,6-xylenol, for example, using a complex of a cuprous salt and anamine as a catalyst, and methods described in U.S. Pat. No. 3,306,875 A,U.S. Pat. No. 3,257,357 A, U.S. Pat. No. 3,257,358 A. JP S52-17880 B, JP$50-51197 A, and JP S63-152628 A.

—Modified Polyphenylene Ether—

The modified polyphenylene ether may be, but is not specifically limitedto, a modified polyphenylene ether obtained through grafting or additionof a styrene polymer or derivative thereof to the polyphenylene etherdescribed above. The percentage mass increase due to grafting oraddition is not specifically limited, but relative to 100 mass % of themodified polyphenylene ether, is preferably 0.01 mass % or more, and ispreferably 10 mass % or less, more preferably 7 mass % or less, andparticularly preferably 5 mass % or less.

The method by which the modified polyphenylene ether is produced is notspecifically limited and may, for example, be a method in which thepolyphenylene ether described above and a styrene polymer or derivativethereof are caused to react in a molten state, solution state, or slurrystate at 80° C. to 350° C. in the presence or absence of a radicalprecursor.

In a case in which the polyphenylene ether resin (I) used in the presentembodiment is a mixture of a polyphenylene ether and a modifiedpolyphenylene ether, the mixing ratio of the polyphenylene ether and themodified polyphenylene ether may be any ratio without any specificlimitations.

—Polypropylene Resin (II)—

The polypropylene resin (II) used in the present embodiment may be, butis not specifically limited to, a polypropylene, a modifiedpolypropylene, or a mixture of both. Component (II) may be one type usedindividually, or two or more types used in combination.

From a viewpoint of inhibiting draw-down during burning and improvingthe balance of fluidity and mechanical strength of the resincomposition, the weight average molecular weight (Mw) of component (II)is preferably 400,000 or more, more preferably 700,000 or more, andparticularly preferably 750,000 or more, and is preferably 1,500,000 orless, and more preferably 1,300,000 or less.

The weight average molecular weight (Mw) can be determined by gelpermeation chromatography (hereinafter, also referred to as “GPC”)according to a conventional and commonly known method. Although nospecific limitations are made, the mobile phase in the GPC may, forexample, be o-dichlorobenzene and the standard material in the GPC may,for example, be polystyrene. More specifically, the weight averagemolecular weight (Mw) can be measured by a method described in thesubsequent EXAMPLES section.

—Polypropylene—

The polypropylene may be, but is not specifically limited to, ahomopolymer or copolymer having propylene as a repeating unit structure.A crystalline propylene homopolymer, a crystalline propylene-ethyleneblock copolymer, or a mixture of a crystalline propylene homopolymer anda crystalline propylene-ethylene block copolymer is preferable.

The crystalline propylene-ethylene block copolymer may be, but is notspecifically limited to, a block copolymer having a crystallinepropylene homopolymer portion and a propylene-ethylene random copolymerportion.

From a viewpoint of inhibiting draw-down during burning and improvingthe balance of fluidity and mechanical strength of the resincomposition, the melt flow rate (hereinafter, also referred to as the“MFR”) of the polypropylene is preferably 0.1 g/10 min or more, and morepreferably 0.3 g/10 min or more, and is preferably 10 g/10 min or less,more preferably 6 g/10 min or less, and particularly preferably 3 g/10min or less.

The MFR can be measured in accordance with ISO 1133 under conditions ofa temperature of 230° C. and a load of 2.16 kg. More specifically, theMFR can be measured by a method described in the subsequent EXAMPLESsection.

The method by which the polypropylene is produced is not specificallylimited and may be a commonly known method.

Specific examples of polypropylene production methods that can be usedinclude a method in which propylene is polymerized at a temperature of0° C. to 100° C. and a pressure of 3 atm to 100 atm in the presence of apolymerization catalyst composition containing an alkyl aluminumcompound and a titanium trichloride catalyst or a halogenated titaniumcatalyst or the like supported on a support such as magnesium chloride.

In this method, a chain transfer agent such as hydrogen may be added toadjust the molecular weight of the polymer.

Moreover, besides the polymerization catalyst composition, an electrondonor compound may be further contained in the polymerization system inthis method as an internal donor component or an external donorcomponent to increase isotacticity of the resultant polypropylene andpolymerization activity of the polymerization system. The electron donorcompound that is used in not specifically limited and may be a commonlyknown electron donor compound. Specific examples of electron donorcompounds that can be used include ester compounds such asε-caprolactone, methyl methacrylate, ethyl benzoate, and methyl toluate;phosphite esters such as triphenyl phosphite and tributyl phosphite;phosphoric acid derivatives such as hexamethylphosphoric triamide;alkoxy ester compounds; esters of aromatic monocarboxylic acids;aromatic alkylalkoxysilanes; aliphatic hydrocarbon alkoxysilanes;various ether compounds; various alcohols; and various phenols.

The polymerization process in the above method may be a batch process ora continuous process. Moreover, the polymerization method may, forexample, be solution polymerization or slurry polymerization using asolvent such as butane, pentane, hexane, heptane, or octane, bulkpolymerization in the monomer without a solvent, or gas-phasepolymerization in a gaseous polymer.

Among polypropylene production methods, the method by which acrystalline propylene-ethylene block copolymer, in particular, isproduced may be, but is not specifically limited to, a method includinga first step of obtaining a crystalline propylene homopolymer portionand a second step of obtaining a propylene-ethylene copolymer portionbonded to the crystalline propylene homopolymer portion throughcopolymerization of the crystalline propylene homopolymer portion withethylene and other α-olefins added as necessary. No specific limitationsare placed on other α-olefins that may be used and examples thereofinclude propylene, 1-butene, and 1-hexene.

—Modified Polypropylene—

The modified polypropylene may be, but is not specifically limited to, amodified polypropylene obtained through grafting or addition of anα,β-unsaturated carboxylic acid or a derivative thereof (for example, anacid anhydride or ester) to the polypropylene described above. Thepercentage mass increase due to the grafting or addition is notspecifically limited, but relative to 100 mass % of the modifiedpolypropylene, is preferably 0.01 mass % or more, and is preferably 10mass % or less, more preferably 7 mass % or less, and particularlypreferably 5 mass % or less.

The method by which the modified polypropylene is produced is notspecifically limited and may, for example, be a method in which thepolypropylene described above and an α,β-unsaturated carboxylic acid orderivative thereof are caused to react in a molten state, solutionstate, or slurry state at 30° C. to 350° C. in the presence or absenceof a radical precursor.

In a case in which the polypropylene resin (II) used in the presentembodiment is a mixture of a polypropylene and a modified polypropylene,the mixing ratio of the polypropylene and the modified polypropylene maybe any ratio without any specific limitations.

—Hydrogenated Block Copolymer (III)—

The hydrogenated block copolymer resin (III) used in the presentembodiment may be, but is not specifically limited to, an unmodifiedhydrogenated block copolymer, a modified hydrogenated block copolymer,or a mixture of both. Component (III) may be one type used individually,or two or more types used in combination.

Component (III) acts as a mixing agent or impact resistance impartingagent for the components (I) and (II).

The hydrogenated block copolymer resin (III) is a product obtainedthrough at least partial hydrogenation of a block copolymer including apolymer block A of mainly a vinyl aromatic compound and a polymer blockB of mainly a conjugated diene compound. The total amount of 1,2-vinylbonding and 3,4-vinyl bonding in the conjugated diene compound of thepolymer block B (hereinafter, also referred to as the “total amount ofvinyl bonding”; described further below) is 30% to 90%.

The following describes matter relating to the modified and unmodifiedhydrogenated block copolymers.

—Polymer Block a of Mainly Vinyl Aromatic Compound—

The polymer block A of mainly a vinyl aromatic compound may be, but isnot specifically limited to, a homopolymer block of a vinyl aromaticcompound or a copolymer block of a vinyl aromatic compound and aconjugated diene compound.

Note that “mainly of a vinyl aromatic compound” in the case of thepolymer block A means that the content of a vinyl aromatic compoundportion in the polymer block A prior to hydrogenation is more than 50mass %. This content is preferably 70 mass % or more, and morepreferably 80 mass % or more, and may be 100 mass % or less.

Examples of the vinyl aromatic compound forming the polymer block Ainclude, but are not specifically limited to, styrene, α-methylstyrene,vinyltoluene, p-tert-butylstyrene, and diphenylethylene. The vinylaromatic compound is preferably styrene. One vinyl aromatic compound maybe used individually, or two or more vinyl aromatic compounds may beused in combination.

From a viewpoint of improving heat creeping-resistance of the resincomposition, the number average molecular weight (Mn) of the polymerblock A is preferably 15,000 or more, more preferably 20,000 or more,and particularly preferably 25,000 or more, and is preferably 100,000 orless.

The number average molecular weight (Mn) can be determined by GPC(mobile phase: chloroform; standard material: polystyrene) according toa conventional and commonly known method. More specifically, the numberaverage molecular weight (Mn) can be measured by a method described inthe subsequent EXAMPLES section.

—Polymer Block B of Mainly Conjugated Diene Compound—

The polymer block B of mainly a conjugated diene compound may be, but isnot specifically limited to, a homopolymer block of a conjugated dienecompound or a copolymer block of a conjugated diene compound and a vinylaromatic compound.

Note that “mainly of a conjugated diene compound” in the case of thepolymer block B means that the content of a conjugated diene compoundportion of the polymer block B prior to hydrogenation is more than 50mass %. From a viewpoint of increasing fluidity of the resincomposition, this content is preferably 70 mass % or more, and morepreferably 80 mass % or more, and may be 100 mass % or less.

Examples of the conjugated diene compound forming the polymer block Binclude, but are not specifically limited to, butadiene, isoprene,1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. The conjugated dienecompound is preferably butadiene, isoprene, or a combination thereof,and is more preferably butadiene. One conjugated diene compound may beused individually, or two or more conjugated diene compounds may be usedin combination.

From a viewpoint of increasing compatibility of the polymer block B withcomponent (II), the total amount of 1,2-vinyl bonding and 3,4-vinylbonding in the microstructure (conjugated diene compound bonding mode)of the polymer block B is 30% or more, preferably 45% or more, and morepreferably 65% or more, and is 90% or less.

The total amount of 1,2-vinyl bonding and 3,4-vinyl bonding (totalamount of vinyl bonding) refers to the total amount of 1,2-vinyl bondingand 3,4-vinyl bonding in the polymer block B prior to hydrogenation as aproportion relative to the total amount of 1,2-vinyl bonding, 3,4-vinylbonding, and 1,4-conjugated bonding. The total amount of vinyl bondingcan be determined through measurement using an infraredspectrophotometer and calculation in accordance with the methoddescribed in Analytical Chemistry, Volume 21, No. 8, August 1949.

The method by which the block copolymer including the polymer block Aand the polymer block B is synthesized is not specifically limited andmay, for example, be a commonly known method such as anionicpolymerization.

The block structure of the block copolymer of the modified andunmodified hydrogenated block copolymers is not specifically limited.For example, a structure such as A-B, A-B-A, B-A-B-A, (A-B-)₄M, orA-B-A-B-A, where “A” represents polymer block A and “B” representspolymer block B, may be used as component (III). Note that (A-B-)₄M is areaction residue of a polyfunctional coupling agent such as silicontetrachloride (M=Si) or tin tetrachloride (M=Sn), a residue of aninitiator such as a polyfunctional organolithium compound, or the like.

The molecular structure of the block copolymer of the modified andunmodified hydrogenated block copolymers is not specifically limited andmay, for example, be a linear structure, a branched structure, a radialstructure, or a combination of these structures.

Moreover, the distribution of the vinyl aromatic compound in themolecular chain of the polymer block A included in the block copolymerand the distribution of the conjugated diene compound in the molecularchain of the polymer block B included in the block copolymer are notspecifically limited and may, for example, be a random distribution, atapered distribution (i.e., a distribution in which monomer portionsincrease or decrease along the molecular chain), a partial block-shapeddistribution, or a combination of these distributions.

In a case in which the block copolymer includes a plurality of polymerblocks A or polymer blocks B, these polymer blocks A or polymer blocks Bmay each have the same structure or may have different structures.

With regards to the overall block copolymer including the polymer blockA and the polymer block B, from a viewpoint of improving fluidity,impact resistance, and external appearance of the hydrogenated blockcopolymer (III) and reducing weld formation, the vinyl aromatic compoundcontent in the block copolymer prior to hydrogenation is preferably 20mass % or more, and more preferably 30 mass % or more, and is preferably95 mass % or less, and more preferably 80 mass % or less.

The content of the vinyl aromatic compound can be measured using anultraviolet spectrophotometer.

The number average molecular weight (Mn) of the block copolymer prior tohydrogenation is preferably 5,000 or more, more preferably 10,000 ormore, and particularly preferably 30,000 or more, and is preferably1,000,000 or less, more preferably 800,000 or less, and particularlypreferably 500,000 or less.

The number average molecular weight can be measured by GPC (mobilephase: chloroform; standard material: polystyrene) according to aconventional and commonly known method.

The molecular weight distribution (Mw/Mn) of the block copolymer priorto hydrogenation is preferably 10 or less, more preferably 8 or less,and particularly preferably 5 or less.

The molecular weight distribution (Mw/Mn) can be calculated bydetermining the weight average molecular weight (Mw) by GPC (mobilephase: chloroform; standard material: polystyrene) according to aconventional and commonly known method, and then dividing the weightaverage molecular weight (Mw) by the number average molecular weight(Mn).

The method by which the block copolymer is hydrogenated is notspecifically limited and may, for example, be a method in whichhydrogenation is performed under conditions of a reaction temperature of0° C. to 200° C. and a hydrogen pressure of 0.1 MPa to 15 MPa using (1)a supported heterogeneous hydrogenation catalyst of a metal such as Ni,Pt, Pd, or Ru supported on carbon, silica, alumina, diatomaceous earth,or the like, (2) a Ziegler-type hydrogenation catalyst in which atransition metal salt such as an organic acid salt or acetylacetonatesalt of Ni, Co, Fe, Cr, or the like and a reducing agent such as anorganoaluminum reducing agent are used, or (3) a homogeneoushydrogenation catalyst in which a organometallic compound of Ti, Ru, Rh,Zr, or the like, referred to as an organometallic complex, is used.

The hydrogenation rate of the conjugated diene compound portion of thepolymer block B in the modified and unmodified hydrogenated blockcopolymers is not specifically limited, but from a viewpoint ofincreasing heat resistance of the resin composition, is preferably 50%or more, more preferably 80% or more, and particularly preferably 90% ormore relative to the total number of double bonds originating from theconjugated diene compound.

The hydrogenation rate can be measured using a nuclear magneticresonance (NMR) spectrometer.

The method by which the modified and unmodified hydrogenated blockcopolymers are produced is not specifically limited and may be acommonly known method. Specific examples of commonly known productionmethods that can be used include those described in JP S47-11486 A, JP$49-66743 A, JP $50-75651 A, JP $54-126255 A, JP S56-10542 A, JPS56-62847 A, JP 556-100840 A. JP H02-300218 A, GB 1130770 A, U.S. Pat.No. 3,281,383 A, U.S. Pat. No. 3,639,517 A, GB 1020720 A, U.S. Pat. No.3,333,024 A, and U.S. Pat. No. 4,501,857 A.

The following describes matter relating particularly to the modifiedhydrogenated block copolymer.

(Modified Hydrogenated Block Copolymer)

The modified hydrogenated block copolymer is a product obtained throughgrafting or addition of an α,β-unsaturated carboxylic acid or aderivative thereof (for example, an acid anhydride or an ester) to theunmodified hydrogenated block copolymer described above.

The percentage mass increase due to the grafting or addition is notspecifically limited, but relative to 100 mass % of the unmodifiedhydrogenated block copolymer, is preferably 0.01 mass % or more, and ispreferably 10 mass % or less, more preferably 7 mass % or less, andparticularly preferably 5 mass % or less.

The method by which the modified hydrogenated block copolymer isproduced is not specifically limited and may, for example, be a methodin which the unmodified hydrogenated block copolymer and anα,β-unsaturated carboxylic acid or derivative thereof are caused toreact in a molten state, solution state, or slurry state at 80° C. to350° C. in the presence or absence of a radical precursor.

—Phosphate Ester Compound (IV)—

The phosphate ester compound (IV) that may optionally be used in thepresent embodiment is not specifically limited and any phosphate estercompound (phosphate ester compound, condensed phosphate ester compound,or the like) that has an effect of improving resin composition flameretardance can be used. Examples include triphenyl phosphate, phenylbisdodecyl phosphate, phenyl bisneopentyl phosphate,phenyl-bis(3,5,5′-trimethyl-hexyl phosphate), ethyl diphenyl phosphate,2-ethyl-hexyl di(p-tolyl)phosphate, bis(2-ethylhexyl)-p-tolyl phosphate,tritolyl phosphate, bis(2-ethylhexyl)phenyl phosphate,tri(nonylphenyl)phosphate, di(dodecyl)-p-tolyl phosphate, tricresylphosphate, dibutylphenyl phosphate, 2-chloro-ethyl diphenyl phosphate,p-tolyl bis(2,5,5′-trimethylhexyl)phosphate, 2-ethylhexyl diphenylphosphate, bisphenol A bis(diphenyl phosphate),diphenyl-(3-hydroxyphenyl)phosphate, bisphenol A bis(dicresylphosphate), resorcinol bis(diphenyl phosphate), resorcinol bis(dixylenylphosphate), 2-naphthyl diphenyl phosphate, 1-napthyl diphenyl phosphate,and di(2-naphthyl)phenyl phosphate.

In particular, it is preferable that the phosphate ester compound (IV)has, as a main component, at least one selected from the groupconsisting of aromatic condensed phosphate ester compounds representedby the following formula (4)

[in formula (4), Q⁴¹, Q⁴², Q⁴³, and Q⁴⁴ are each, independently of oneanother, an alkyl group having a carbon number of 1 to 6; R⁴¹ and R⁴²are each, independently of one another, a methyl group; R⁴³ and R⁴⁴ areeach, independently of one another, a hydrogen atom or a methyl group; xis an integer of 0 or more; p₁, p₂, p₃, and p₄ are each an integer of 0to 3; and q₁ and q₂ are each an integer of 0 to 2]

and the following formula (5)

[in formula (5), Q⁵¹, Q⁵², Q⁵³, and Q⁵⁴ are each, independently of oneanother, an alkyl group having a carbon number of 1 to 6; R⁵¹ is amethyl group; y is an integer of 0 or more; r₁, r₂, r₃, and r₄ are eachan integer of 0 to 3; and s₁ is an integer of 0 to 2].

Note that the condensed phosphate ester compounds represented by formula(4) and formula (5) may each include a plurality of types of molecules,and n is preferably an integer of 1 to 3 for each of the molecules.

In a suitable phosphate ester compound (IV) having at least one selectedfrom the group consisting of condensed phosphate ester compoundsrepresented by formula (4) and formula (5) as a main component, overall,the average value of n is preferably 1 or more. This suitable phosphateester compound (IV) can normally be acquired as a mixture containing 90%or more of compounds for which n is 1 to 3, and besides the compoundsfor which n is 1 to 3, also containing polymeric products for which n is4 or more and other by-products.

—Phosphinate Salt (V)—

The phosphinate salt (V) that is used in the present embodiment may, forexample, be at least one selected from the group consisting of:

a phosphinate salt represented by the following formula (1)

[in formula (1), R¹¹ and R¹² are each, independently of one another, alinear or branched alkyl group having a carbon number of 1 to 6 and/oran aryl group having a carbon number of 6 to 10; M¹ is at least oneselected from the group consisting of a calcium ion, a magnesium ion, analuminum ion, a zinc ion, a bismuth ion, a manganese ion, a sodium ion,a potassium ion, and a protonated nitrogenous base; a is an integer of 1to 3; m is an integer of 1 to 3; and a=m]; and

a diphosphinate salt represented by the following formula (2)

[in formula (2), R²¹ and R²² are each, independently of one another, alinear or branched alkyl group having a carbon number of 1 to 6 and/oran aryl group having a carbon number of 6 to 10; R²³ is a linear orbranched alkylene group having a carbon number of 1 to 10, an arylenegroup having a carbon number of 6 to 10, an alkylarylene group having acarbon number of 6 to 10, or an arylalkylene group having a carbonnumber of 6 to 10; M² is at least one selected from the group consistingof a calcium ion, a magnesium ion, an aluminum ion, a zinc ion, abismuth ion, a manganese ion, a sodium ion, a potassium ion, and aprotonated nitrogenous base; b is an integer of 1 to 3; n is an integerof 1 to 3; j is an integer of 1 or 2; and b·j=2n].

Moreover, the phosphinate salt (V) may be a mixture of a phosphinatesalt represented by formula (1) and a diphosphinate salt represented byformula (2).

Examples of such phosphinate salts (V) include, but are not specificallylimited to, calcium dimethylphosphinate, magnesium dimethylphosphinate,aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethyl phosphinate, magnesium ethylmethylphosphinate, aluminumethylmethylphosphinate, zinc ethylmethylphosphinate, calciumdiethylphosphinate, magnesium diethylphosphinate, aluminumdiethylphosphinate, zinc diethylphosphinate, calciummethyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate,aluminum methyl-n-propylphosphinate, zinc methyl-n-propylphosphinate,calcium methane di(methylphosphinate), magnesium methanedi(methylphosphinate), aluminum methane di(methylphosphinate), zincmethane di(methylphosphinate), calciumbenzene-1,4-(dimethylphosphinate), magnesiumbenzene-1,4-(dimethylphosphinate), aluminumbenzene-1,4-(dimethylphosphinate), zincbenzene-1,4-(dimethylphosphinate), calcium methylphenylphosphinate,magnesium methylphenylphosphinate, aluminum methylphenylphosphinate,zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesiumdiphenylphosphinate, aluminum diphenylphosphinate, and zincdiphenylphosphinate. The phosphinate salt (V) is preferably calciumdimethylphosphinate, aluminum dimethylphosphinate, zincdimethylphosphinate, calcium ethylmethylphosphinate, aluminumethylmethylphosphinate, zinc ethylmethylphosphinate, calciumdiethylphosphinate, aluminum diethylphosphinate, or zincdiethylphosphinate, and more preferably aluminum diethylphosphinate.

Examples of commercially available products that can be used as thephosphinate salt (V) include, but are not specifically limited to,Exolit® (Exolit is a registered trademark in Japan, other countries, orboth) OP1230, OP1240, OP1311, OP1312. OP930, and OP935 produced byClariant (Japan) K.K.

—Thermoplastic Resin (VI) Other than Components (I) and (II)—

Examples of thermoplastic resins (VI) other than components (I) and (II)that may optionally be used in the present embodiment include, but arenot specifically limited to, polystyrene, syndiotactic polystyrene, andhigh impact polystyrene.

—Additive (VII) Other than Components (I) to (VI)—

Examples of additives (VII) other than components (I) to (VI) that mayoptionally be used in the present embodiment include, but are notspecifically limited to, vinyl aromatic compound-conjugated dienecompound block copolymers, olefin elastomers, antioxidants, metaldeactivators, heat stabilizers, flame retardants other than components(IV) and (V) (for example, ammonium polyphosphate compounds, magnesiumhydroxide, aromatic halogen-containing flame retardants, silicone flameretardants, and zinc borate), fluorine-containing polymers, plasticizers(for example, low molecular weight polyethylene, epoxidized soybean oil,polyethylene glycol, and esters of fatty acids), flame retardantsynergists such as antimony trioxide, weather (light) resistancemodifiers, nucleating agents for polyolefins, slip agents, organic orinorganic fillers or reinforcers other than component (IV) (for example,carbon black, titanium oxide, calcium carbonate, mica, kaolin, glassfiber, glass flake, and conductive carbon black), various colorants, andmold release agents.

The following describes the proportions of components in the resincomposition of the present embodiment.

From a viewpoint of increasing flame retardance, chemical resistance,and shaping fluidity of the resin composition, the content of component(I) in the resin composition of the present embodiment, relative to 100parts by mass, in total, of components (I) and (II), is 40 parts by massor more, preferably 50 parts by mass or more, and more preferably 65parts by mass or more, and is 99 parts by mass or less, preferably 80parts by mass or less, and more preferably 75 parts by mass or less.

Moreover, from a viewpoint of increasing flame retardance, chemicalresistance, and shaping fluidity of the resin composition, the contentof component (II) in the resin composition of the present embodiment,relative to 100 parts by mass, in total, of components (I) and (II), is1 part by mass or more, preferably 20 parts by mass or more, and morepreferably 25 parts by mass or more, and is 60 parts by mass or less,preferably 50 parts by mass or less, and more preferably 35 parts bymass or less.

Furthermore, from a viewpoint of increasing flame retardance, chemicalresistance, and shaping fluidity of the resin composition, the contentof component (III) in the resin composition of the present embodiment,relative to 100 parts by mass, in total, of components (I) and (II), is1 part by mass or more, preferably 2 parts by mass or more, morepreferably 3 parts by mass or more, and particularly preferably 5 partsby mass or more, and from a viewpoint of preventing detachment from ashaped piece, is 20 parts by mass or less, and preferably 15 parts bymass or less.

Also, from a viewpoint of increasing flame retardance, chemicalresistance, and shaping fluidity of the resin composition in a goodbalance, the content of component (IV) in the resin composition of thepresent embodiment is 5 parts by mass or more, and preferably 10 partsby mass or more, and is 45 parts by mass or less, and preferably 30parts by mass or less.

Moreover, from a viewpoint of increasing flame retardance of the resincomposition, the content of component (V) in the resin composition ofthe present embodiment is preferably 3 parts by mass or more, and morepreferably 4 parts by mass or more, and is preferably 15 parts by massor less, and more preferably 12 parts by mass or less.

Furthermore, the content of component (VI) in the resin composition ofthe present embodiment is not specifically limited so long as theeffects disclosed herein are not lost and may, for example, be 0 partsby mass to 400 parts by mass.

In the resin composition of the present embodiment, a ratio(IV)_((I))/(IV)_((II)) of content (IV)_((I)) of the phosphate estercompound (IV) present in a fraction that dissolves in chloroformrelative to content (IV)_((II)) of the phosphate ester compound (IV)present in a fraction that dissolves in o-dichlorobenzene is 10 or morefrom a viewpoint of improving smoke generation properties and chemicalresistance of the resin composition. This ratio (IV)_((I))/(IV)_((II))is preferably 15 or more, and more preferably 20 or more, and ispreferably 250 or less, more preferably 199 or less, even morepreferably 99 or less, and particularly preferably 50 or less.

More specifically, (IV)_((I)) and (IV)_((II)), can be calculated by thefollowing procedure.

First, the resin composition of the present embodiment is dissolved inchloroform to obtain a chloroform fraction. The polyphenylene etherresin (I), the hydrogenated block copolymer (III), and the like dissolvein the chloroform, but almost none of the polypropylene resin (II)dissolves. Next, a residue fraction that remains without dissolving inthe chloroform is dissolved in o-dichlorobenzene to obtain ano-dichlorobenzene fraction. The polypropylene resin (II) and the likethat do not dissolve in the chloroform dissolve in theo-dichlorobenzene. Thereafter, methanol is used to performreprecipitation with respect to the o-dichlorobenzene solution. In thisreprecipitation, it is mainly resin components such as the polypropyleneresin (II) that reprecipitate and not non-resin components. The content(IV)_((I)) of the phosphate ester compound (IV) present in thechloroform fraction and the content (IV)_((II)) of the phosphate estercompound (IV) present in the reprecipitated product are calculated bymeasuring the absolute mass of the phosphate ester compound (IV)contained in the chloroform fraction and reprecipitated product obtainedin this manner (for example, measurement of the concentration of aphosphorus component contained in the chloroform fraction and thereprecipitated product by inductively coupled plasma mass spectrometry(ICP-MS)).

Examples of techniques by which the partition ratio of (IV)_((I)) and(IV)_((II)) can be controlled include a technique in which, inproduction of the resin composition described further below, thepolypropylene resin (II) is fed into an extruder in a partitioned mannerfrom a plurality of raw material feeding inlets, a technique in which atemperature profile of a kneading machine in melt-kneading is adjusted,a technique in which the timing of addition of component (IV) isadjusted, and a method in which the positioning of kneading discs inbarrel screw configuration is optimized.

(Morphology of Resin Composition)

From a viewpoint of expression of chemical resistance, the morphology inthe resin composition of the present embodiment is preferably amorphology in which a polyphenylene ether resin (I) phase and apolypropylene resin (II) phase are co-continuous or a morphology inwhich a polypropylene resin (II) phase forms a matrix, and is morepreferably a morphology in which a polypropylene resin (II) phase formsa matrix. The polyphenylene ether resin (I) phase is a phase thatcontains the polyphenylene ether resin (I) and may be composed of thepolyphenylene ether resin (I). The polypropylene resin (II) phase is aphase that contains the polypropylene resin (II) and may be composed ofthe polypropylene resin (II).

Methods by which the morphology may be controlled to obtain a morphologysuch as described above include a method in which the compounding ratioof the polyphenylene ether resin (I), the polypropylene resin (II), andthe phosphate ester compound (IV) is adjusted and in which thepolypropylene resin (II) is fed into an extruder in a partitioned mannerfrom a plurality of raw material feeding inlets.

Note that the morphology of the resin composition can be observed usinga transmission electron microscope (TEM) or the like.

(Production Method of Resin Composition)

The resin composition of the present embodiment can be produced bymelt-kneading the components (I) to (IV) set forth above, and also thecomponents (V) to (VII) as necessary.

No specific limitations are placed on the production method of the resincomposition of the present embodiment so long as the components (I) to(IV), and also the components (V) to (VII) as necessary, can bemelt-kneaded.

One suitable production method for the resin composition of the presentembodiment includes a step (1-1) of melt-kneading all of component (I)and all or some of components (II) and (III) to obtain a kneadedproduct, a step (1-2) of adding the remainder of components (II) and(III) to the kneaded product obtained in step (1-1) (excluding a case inwhich all of components (II) and (III) are added in step (1-1)) andperforming further melt-kneading to obtain a kneaded product, and a step(1-3) of adding all of component (IV) to the kneaded product obtained instep (1-2) and performing further melt-kneading.

A suitable production method for the resin composition of the presentembodiment may be a method in which melt-kneading is performed overmultiple stages. These multiple stages are not specifically limitedother than being two or more stages.

This method in the present embodiment may, for example, include a stepin which all of component (I), some of component (II), all of component(Ill), and all of component (IV) are melt-kneaded in a first stage toobtain pellets, and a step in which the pellets obtained in the firststage, the remainder of component (II), and, as necessary, components(I) to (VII) are added and further melt-kneaded in a second stage. Insuch a case, all of component (II) may alternatively be added in thesecond stage.

Moreover, another suitable production method for the resin compositionof the present embodiment is a masterbatch method in which a resincomposition (masterbatch) containing specific components in a highconcentration is prepared in advance, and the masterbatch issubsequently diluted to obtain a resin composition containing eachcomponent in a desired concentration.

This method in the present embodiment may, for example, include a stepin which all of component (I), some of component (II), all of component(III), and all of component (IV) are melt-kneaded in a first stage toobtain masterbatch pellets containing component (IV) in a higherconcentration than in the final composition, and a step in which themasterbatch pellets, the remainder of component (II), and, as necessary,components (V) to (VII) are added and further melt-kneaded in a secondstage to obtain the final composition. In this case, all of component(II) may alternatively be added in the second stage.

Examples of melt-kneading machines that can suitably be used to performmelt-kneading of the components in a production method such as set forthabove include, but are not specifically limited to, heated melt-kneadingmachines such as an extruder (for example, a single screw extruder or amultiscrew extruder such as a twin screw extruder), a roller, a kneader,a Brabender Plastograph, and a Banbury mixer. In particular, a twinscrew extruder is preferable from a viewpoint of kneading performance.Specific examples of twin screw extruders that can be used include theZSK series produced by Coperion Inc., the TEM series produced by ToshibaMachine Co., Ltd., and the TEX series produced by The Japan Steel Works,Ltd.

The following describes a preferred embodiment of a case in which anextruder such as a single screw extruder, twin screw extruder, or othermultiscrew extruder is used.

The type, specifications, and so forth of the extruder are notspecifically limited and may be commonly known examples thereof.

L/D of the extruder (barrel effective length/barrel internal diameter)is preferably 20 or more, and more preferably 30 or more, and ispreferably 75 or less, and more preferably 60 or less.

The extruder preferably has a configuration including different rawmaterial feeding inlets at two or more locations, vacuum vents at two ormore locations, and liquid addition pumps (described further below) atone or more locations. In terms of positioning of the equipmentdescribed above, from a viewpoint of density of generated smoke andexpression of chemical resistance, it is more preferable that, in thedirection of raw material flow, a first raw material feeding inlet islocated at an upstream side, a first vacuum vent is located furtherdownstream than the first raw material feeding inlet, a second rawmaterial feeding inlet is located further downstream than the firstvacuum vent, a liquid addition pump is located further downstream thanthe second raw material feeding inlet, and a second vacuum vent islocated further downstream than the liquid addition pump.

The method by which a raw material is fed at the second raw materialfeeding inlet is not specifically limited and may be a method in whichthe raw material is simply added from an opening in an upper part of theraw material feeding inlet or a method in which the raw material isadded from a side opening using a forced side feeder. In particular, amethod in which the raw material is added from a side opening using aforced side feeder is preferable from a viewpoint of stable feeding.

The melt-kneading temperature in melt-kneading of the components maynormally be 270° C. to 320° C.

In particular, it is preferable that the temperature between the firstraw material feeding inlet and the second raw material feeding inlet isset as at least 300° C. and not higher than 320° C. from a viewpoint ofexpression of smoke generation properties and chemical resistance of theresin composition.

Moreover, from a viewpoint of expression of smoke generation propertiesand chemical resistance of the resin composition, it is preferable thatthe set temperature for between the first raw material feeding inlet andthe second raw material feeding inlet and the set temperature for asection further downstream than the second raw material feeding inletdiffer from one another. Specifically, it is preferable that the settemperature for between the first raw material feeding inlet and thesecond raw material feeding inlet is at least 300° C. and not higherthan 320° C., and that the set temperature for the section furtherdownstream than the second raw material feeding inlet is at least 270°C. and lower than 300° C.

The configuration of a screw included in a barrel is not specificallylimited and may be a configuration in which right-handed, left-handed,orthogonal (N-type), and back-conveying (L-type) kneading disc elementsare provided as appropriate. In particular, a configuration in which atleast one orthogonal (N-type) kneading disc element and at least oneback-conveying (L-type) kneading disc element are provided between thefirst raw material feeding inlet and the second raw material feedinginlet, and in which at least one orthogonal (N-type) kneading discelement is provided between the liquid addition pump and the vacuum ventlocated further downstream than the liquid addition pump is preferablesince this configuration enables control of the dispersion state of thephosphate ester compound (IV) to within a specific range.

Although no specific limitations are placed on the screw rotation speed,the screw rotation speed may normally be 100 rpm to 1,200 rpm, and ispreferably 200 rpm to 700 rpm from a viewpoint of smoke generationproperties and expression of chemical resistance.

In a case in which a liquid raw material is to be added, the liquid rawmaterial can be added by using a liquid addition pump or the like in acylinder section of the extruder to directly feed the liquid rawmaterial into the cylinder. The liquid addition pump may be, but is notspecifically limited to, a gear pump, a flange pump, or the like, and ispreferably a gear pump. In this case, from a viewpoint of reducing theload on the liquid addition pump and improving raw material operability,it is preferable to lower the viscosity of the liquid raw material byusing a heater or the like to heat a tank in which the liquid rawmaterial is stored or a section that forms a flow path of the liquid rawmaterial, such as piping between the tank and the liquid addition pumpand piping between the pump and the extruder cylinder.

In terms of the addition position of the phosphate ester compound (IV),a ratio L1/L of the length L1 from the first raw material feeding inletto the addition position of the phosphate ester compound relative to thetotal barrel effective length L is preferably 0.2 to 0.75 since thisenables control of the dispersion state of the phosphate ester compound(IV) to within a specific range. The value of L1/L is more preferably0.25 to 0.7, and even more preferably 0.3 to 0.6.

(Shaped Product)

A shaped product of the present embodiment is formed from the resincomposition of the present embodiment set forth above.

The shaped product of the resin composition of the present embodiment isnot specifically limited and examples thereof include automotivecomponents, interior and exterior components of electrical devices,other components, and so forth. Examples of automotive componentsinclude, but are not specifically limited to, exterior components suchas bumpers, fenders, door panels, various moldings, emblems, enginehoods, wheel caps, roofs, spoilers, and various aero parts; interiorcomponents such as instrument panels, console boxes, and trims; batterycase components for secondary batteries installed in vehicles, electricvehicles, hybrid electric vehicles, and the like; and lithium ionsecondary battery components. Examples of interior and exteriorcomponents of electrical devices include, but are not specificallylimited to, components used in various computers and peripheralequipment thereof, other office automation equipment, televisions, videorecorders, cabinets for various disc players, chassis, refrigerators,air conditioners, and LCD projectors. Examples of other componentsinclude wires and cables obtained by applying a coating on a metalconductor or optical fiber, fuel cases for solid methanol batteries,water pipes for fuel cells, water cooling tanks, boiler exterior cases,ink peripheral components and parts for inkjet printers, furniture(chairs, etc.), chassis, water piping, and joints.

(Production Method of Shaped Product)

The shaped product of the present embodiment can be produced throughshaping of the resin composition of the present embodiment set forthabove.

The production method of the shaped product of the present embodimentmay be, but is not specifically limited to, injection molding, extrusionmolding, profile extrusion molding, blow molding, compression molding,or the like, and is preferably injection molding from a viewpoint ofmore effectively obtaining the effects disclosed herein.

Examples

The following describes embodiments of this disclosure based onexamples, but this disclosure is not limited to these examples.

Raw materials used for resin compositions and shaped products in theexamples and comparative examples were as follows.

—Polyphenylene Ether Resin (I)—

(I-i): Polyphenylene ether obtained through oxidative polymerization of2,6-xylenol and having a reduced viscosity (ηsp/c: 0.5 g/dL chloroformsolution) of 0.33

(I-ii): Polyphenylene ether obtained through oxidative polymerization of2,6-xylenol and having a reduced viscosity (ηsp/c: 0.5 g/dL chloroformsolution) of 0.42

Note that the reduced viscosity was measured as ηsp/c of a 0.5 g/dLchloroform solution at a temperature of 30° C.

—Polypropylene Resin (II)—

(II-i): Polypropylene homopolymer having an MFR of 0.4 g/10 min

(II-ii): Polypropylene homopolymer having an MFR of 5.9 g/10 min

(II-iii): Polypropylene homopolymer having an MFR of 15 g/10 min

Note that the MFR was measured in accordance with ISO 1133 underconditions of a temperature of 230° C. and a load of 2.16 kg.

—Hydrogenated Block Copolymer (III)—

(III): Polymer synthesized as described below

A block copolymer having a B-A-B-A block structure in which the polymerblocks A were formed from polystyrene and the polymer blocks B wereformed from polybutadiene was synthesized by a commonly known method.The synthesized block copolymer was hydrogenated by a commonly knownmethod. Polymer modification was not performed. The physical propertiesof the unmodified hydrogenated block copolymer that was obtained were asfollows.

(III-i): B-A-B-A type

Polystyrene content in block copolymer prior to hydrogenation: 44%

Number average molecular weight (Mn) of block copolymer prior tohydrogenation: 95,000

Number average molecular weight (Mn) of polystyrene blocks: 41,800

Number average molecular weight (Mn) of polybutadiene blocks: 53.200

Molecular weight distribution (Mw/Mn) of block copolymer prior tohydrogenation: 1.06

Total amount of vinyl bonding (amount of 1,2-vinyl bonding) inpolybutadiene blocks prior to hydrogenation: 75%

Hydrogenation rate of polybutadiene portion of polybutadiene blocks:99.9%

The vinyl aromatic compound content was measured using an ultravioletspectrophotometer. The number average molecular weight (Mn) wasdetermined by GPC (mobile phase: chloroform; standard material:polystyrene) according to a conventional and commonly known method. Themolecular weight distribution (Mw/Mn) was calculated by determining theweight average molecular weight (Mw) by GPC (mobile phase: chloroform;standard material: polystyrene) according to a conventional and commonlyknown method, and then dividing the weight average molecular weight (Mw)by the number average molecular weight (Mn). The total amount of vinylbonding was determined through measurement using an infraredspectrophotometer and calculation in accordance with the methoddescribed in Analytical Chemistry, Volume 21, No. 8, August 1949. Thehydrogenation rate was measured using a nuclear magnetic resonance (NMR)spectrometer.

—Phosphate Ester Compound (IV)—

(IV): E890 (condensed phosphate ester compound) produced by DaihachiChemical Industry Co., Ltd.

—Phosphinate Salt (V)—

(V): Exolit OP1230 (corresponding to formula (1)) produced by Clariant(Japan) K.K.

The following raw material was used particularly in resin compositionsof the comparative examples.

(III-x): A-B-A type

Polystyrene content in block copolymer prior to hydrogenation: 65%

Number average molecular weight (Mn) of block copolymer prior tohydrogenation: 53,000

Number average molecular weight (Mn) of polystyrene blocks: 34,800

Number average molecular weight (Mn) of polybutadiene blocks: 18.700

Molecular weight distribution (Mw/Mn) of block copolymer prior tohydrogenation: 1.23

Total amount of vinyl bonding (amount of 1,2-vinyl bonding) inpolybutadiene blocks prior to hydrogenation: 9%

Hydrogenation rate of polybutadiene portion of polybutadiene blocks:99.9%

Physical property measurement methods (1) to (4) in the examples andcomparative examples were as follows.

(1) Calculation of Ratio (IV)_((I))/(IV)_((II))

A resin composition produced as described below was sampled into afilter paper thimble in an amount of 2 g and Soxhlet extraction wasperformed for 8 hours at 65° C. to 75° C. using 120 mL of chloroform toseparate a residue fraction (A) on the filter paper thimble and achloroform-soluble fraction (B). The chloroform-soluble fraction (B) wastaken to be a fraction of the resin composition that dissolves inchloroform.

With respect to the residue fraction (A) on the filter paper thimble, 50mL of 150° C. o-dichlorobenzene was added and high-temperaturecentrifugal separation (150° C., twice for 30 minutes at 12,000 rpm) wasperformed to separate a residue fraction (C) and ano-dichlorobenzene-soluble fraction (D). The o-dichlorobenzene-solublefraction (D) was further subjected to reprecipitation through additionof methanol to separate a methanol-insoluble fraction (E) and amethanol-soluble fraction (F). The finally obtained methanol-insolublefraction (E) was taken to be a fraction of the resin composition thatdissolves in o-dichlorobenzene.

The concentration of a phosphorus component extracted in thechloroform-soluble fraction (B) and the methanol-insoluble fraction (E)obtained through this operation was measured by inductively coupledplasma mass spectrometry (ICP-MS). The measured phosphorus componentconcentration was used to calculate the absolute mass of component (IV)present in the soluble fraction (B) and the absolute mass of component(IV) present in the insoluble fraction (E). These calculated absolutemasses were taken to be the content (IV)_((I)) of component (IV) presentin a fraction of the resin composition that dissolves in chloroform andthe content (IV)_((II)) of component (IV) present in a fraction of theresin composition that dissolves in o-dichlorobenzene. Moreover, theratio (IV)_((I))/(IV)_((II)) of (IV)_((I)) relative to (IV)_((II)) wascalculated.

Since polyphenylene ether dissolves in chloroform and polypropylenedissolves in o-dichlorobenzene but does not dissolve in chloroform,(IV)_((I)) indirectly indicates the content of phosphate ester inpolyphenylene ether and (IV)_((II)) indirectly indicates the content ofphosphate ester in polypropylene.

(2) Smoke Generation Properties

The generated-smoke density of obtained resin composition pellets wasmeasured in accordance with ASTM D662 (flaming mode), and the amount ofsmoke generation (Ds) was measured. In terms of evaluation criteria, alower measured value was judged to indicate better smoke generationproperties.

(3) Electrolysis Solution-Resistance

A solution (electrolysis solution) prepared by dissolving lithiumhexafluorophosphate in a mixed solution of 1:1:1 ethylenecarbonate:propylene carbonate:diethylene carbonate such as to have aconcentration of 1 mol/L was used as an immersion test solution.

Obtained resin pellets were fed into a small-size injection moldingmachine (product name: IS-100GN; produced by Toshiba Machine Co., Ltd.)set to a cylinder temperature of 250° C. and were molded underconditions of a mold temperature of 70° C., an injection pressure of 70MPa, an injection time of 20 seconds, and a cooling time of 15 secondsto prepare an ISO dumbbell-shaped specimen for evaluation.

The prepared dumbbell-shaped specimen was immersed in the immersion testsolution for 300 hours at 60° C. and was subsequently removed from theimmersion test solution. The tensile strength of the dumbbell-shapedspecimen after immersion was measured in accordance with ISO 527-1. Thetensile strength of the dumbbell-shaped specimen after immersion as aproportion relative to the tensile strength of a dumbbell-shapedspecimen that had not been treated in the immersion test solution wascalculated as a tensile strength retention rate (indicated in % in thesubsequently described Tables 1 and 2). In terms of evaluation criteria,a higher measured value was judged to indicate a better tensile strengthretention rate and chemical resistance.

(4) Chemical Resistance

Obtained resin pellets were fed into a small-size injection moldingmachine (product name: IS-100GN; produced by Toshiba Machine Co., Ltd.)set to a cylinder temperature of 270° C. and were molded underconditions of a mold temperature of 70° C., an injection pressure of 75MPa, an injection time of 20 seconds, and a cooling time of 15 secondsto obtain a flat plate of 150 mm×150 mm×3 mm.

A specimen of 75 mm×12.7 mm×3 mm was cut out from the flat plate and wasset in a bending form designed to enable continuous variation of strainof the specimen. Chemicals described below were applied onto the surfaceof the specimen and were left for 48 hours under conditions of 23° C.and 50% RH. After 48 hours had passed, strain was applied to thespecimen and the end position of the bending form at which cracking ofthe surface of the specimen occurred was measured to determine thecritical strain (° %), which indicates strain at the limit at whichcracking does not occur. In terms of evaluation criteria, a larger valuefor the critical strain was judged to indicate better chemicalresistance.

The chemicals used in this chemical resistance test were as follows.

-   -   Salad oil (produced by Nisshin Foods)    -   Mold cleaning agent (Super 102C produced by Somax Co., Ltd.)    -   Grease (MOLYCOTE EM-30L produced by Dow Corning Toray)

(5) Flame Retardance

Obtained resin composition pellets were fed into a small-size injectionmolding machine (product name: IS-100GN; produced by Toshiba MachineCo., Ltd.) set to a cylinder temperature of 240° C. and were moldedunder conditions of a mold temperature of 70° C. and an injectionpressure of 60 MPa to prepare five specimens (thickness 1.6 mm) for UL94vertical burning test measurement. The flame retardance of these fivespecimens was evaluated based on the UL94 vertical burning test method.A flame was brought into contact with each specimen for 10 seconds andthen removed, and the burning time until a flame on the specimenextinguished after removal was taken to be t1 (s). Thereafter, a flamewas brought into contact with the specimen for a further 10 seconds andthen removed, and the burning time until a flame on the specimenextinguished after removal was taken to be t2 (s). For each of the fivespecimens, the average value of t1 and t2 was determined as the averageburning time. Moreover, a longest burning time among the 10 measurementsof t1 and t2 was determined as the longest burning time. A judgment ofV-0, V-1, V-2, or HB was made based on UL94 regulations. In particular,a resin composition was judged to be preferable when the flameretardance level was determined to be V-1 or higher.

(6) Morphology

An ultrathin slice of 80 nm in thickness was prepared from an obtainedresin composition pellet using an ultramicrotome, the slice was dyedusing ruthenium tetroxide, and the resultant sample was observed at×10,000 magnification using a TEM (HT7700 produced by HitachiHigh-Technologies Corporation).

The following describes the examples and comparative examples in detail.

A twin screw extruder (ZSK-25 produced by Coperion Inc.) was used as amelt-kneading machine for producing resin compositions in the examplesand comparative examples. L/D of the extruder was 35.

The twin screw extruder had a configuration including, in a direction ofraw material flow, a first raw material feeding inlet located at anupstream side, a second raw material feeding inlet located furtherdownstream than the first raw material feeding inlet, a liquid additionpump located further downstream than the second raw material feedinginlet, and a vacuum vent located between the first raw material feedinginlet and the second raw material feeding inlet. An additional liquidaddition pump and vacuum vent were provided further downstream than thefirst raw material feeding inlet as necessary, and the positions thereofwere appropriately changed as necessary.

The extruder used in the examples and comparative examples had 12barrels and the screw configuration in these barrels was as follows.

-   -   R1-R2-N-N-R3-R3-B (third to fourth barrels in subsequently        described Production Method 1)    -   L (fifth barrel in subsequently described Production Method 1)    -   R2-N-L-R3 (eighth barrel in subsequently described Production        Method 1)    -   R3-R3-N-L-R3 (ninth to eleventh barrels in subsequently        described Production Method 1)

Note that the meanings of abbreviations for kneading discs used todenote the screw configuration are as follows.

-   -   R1: Kneading disc right (L/D=1.44)    -   R2: Kneading disc right (L/D=0.96)    -   R3: Kneading disc right (L/D=0.48)    -   L: Kneading disc left (L/D=0.48)    -   N (N-type): Kneading disc neutral (L/D=1.04)    -   B (L-type): Double flight screw back-conveying (L/D=0.48)

Moreover, resin composition pellets were produced using 7 productionmethods (Production Methods 1 to 7) illustrated in FIG. 1 by alteringthe positions of raw material feeding inlets, vacuum vents, and liquidaddition pumps, the set temperature of each barrel, and the additionposition of component (IV).

Examples 1 to 15 and Comparative Examples 1 to 20

The twin screw extruder set-up as described above was used to melt-kneadcomponents (I) to (V) with the composition and production conditionsshown in Tables 1 and 2 at a discharge rate of 15 kg/hr to produce resincomposition pellets.

In the examples and comparative examples, physical property tests werecarried out by the previously described measurement methods (1) to (4).The results are shown in Tables 1 and 2.

TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 1 ple 2 ple 3 ple4 ple 5 ple 6 ple 7 Resin Component (I) Parts by mass 70 70 70 70 70 7070 composition Component (II) Parts by mass 30 30 30 30 30 30 30Component (III) Parts by mass 10 10 10 10 10 10 10 Component (IV) Partsby mass 15 15 15 15 15 15 15 Component (V) Parts by mass 7 7 0 7 7 7 7Total amount of vinyl % 75 75 75 75 75 75 75 bonding in polymer block Bof component (III) Production method — Produc- Produc- Produc- Produc-Produc- Produc- Produc- tion tion tion tion tion tion tion Meth- Meth-Meth- Meth- Meth- Meth- Meth- od 1 od 2 od 1 od 1 od 1 od 1 od 2 ResinScrew rotation speed rpm 300 300 300 300 300 300 300 composition Firstraw Component (I-i) Parts by mass 70 70 70 70 70 0 0 production materialComponent (I-ii) 0 0 0 0 0 70 70 method feeding Component (II-i) 10 1010 0 0 0 0 inlet Component (II-ii) 0 0 0 10 0 10 10 Component (II-iii) 00 0 0 10 0 0 Component (III-i) 10 10 10 10 10 10 10 Component (III-x) 00 0 0 0 0 0 Second raw Component (II-i) Parts by mass 20 20 20 0 0 0 0material Component (II-ii) 0 0 0 20 0 20 20 feeding Component (II-iii) 00 0 0 20 0 0 inlet Component (V) 7 7 0 7 7 7 7 Liquid Component (IV)Parts by mass 15 15 15 15 15 15 15 addition pump Resin Partition ratio(IV)_((I))/(IV)_((II)) 99.0 130 49.0 32.3 15.7 89.5 117 composition ofcomponent physical (IV) properties Morphology (1) Co-continuouscomponent Yes Yes No No No Yes Yes (I) phase and component (II) phase(2) Component (II) phase No No Yes Yes Yes No No forms matrix (3)Neither of (1) No No No No No No No and (2) applies Physical Smokegeneration Generated-smoke 378 389 265 357 351 366 380 propertyproperties density Ds evaluation Electrolysis Tensile strength 75 72 8577 78 76 74 results solution-resistance retention rate (%) ChemicalSalad oil- Critical strain 0.70 0.69 0.76 0.72 0.72 0.73 0.68 resistanceresistance (%) Mold cleaning 1.63 1.60 1.72 1.62 1.64 1.69 1.55agent-resistance Grease-resistance 1.11 1.09 1.30 1.13 1.15 1.21 1.04Flame retardance Rank V-0 V-0 HB V-0 V-0 V-0 V-0 Exam- Exam- Exam- Exam-Exam- Exam- ple 8 ple 9 ple 10 ple 11 ple 12 ple 13 Resin Component (I)Parts by mass 70 80 60 45 70 70 composition Component (II) Parts by mass30 20 40 55 30 30 Component (III) Parts by mass 10 10 10 10 10 10Component (IV) Parts by mass 15 17 14 15 15 15 Component (V) Parts bymass 7 6 10 7 7 7 Total amount of vinyl % 75 75 75 75 75 75 bonding inpolymer block B of component (III) Production method — Produc- Produc-Produc- Produc- Produc- Produc- tion tion tion tion tion tion Meth-Meth- Meth- Meth- Meth- Meth- od 1 od 1 od 1 od 1 od 2 od 6 Resin Screwrotation speed rpm 300 300 300 300 600 300 composition First rawComponent (I-i) Parts by mass 0 80 60 45 0 0 production materialComponent (I-ii) 70 0 0 0 70 70 method feeding Component (II-i) 10 10 1010 0 0 inlet Component (II-ii) 0 0 0 0 10 10 Component (II-iii) 0 0 0 00 0 Component (III-i) 10 10 10 10 10 10 Component (III-x) 0 0 0 0 0 0Second raw Component (II-i) Parts by mass 20 10 30 45 0 0 materialComponent (II-ii) 0 0 0 0 20 20 feeding Component (II-iii) 0 0 0 0 0 0inlet Component (V) 7 6 10 7 7 7 Liquid Component (IV) Parts by mass 1517 14 15 15 15 addition pump Resin Partition ratio(IV)_((I))/(IV)_((II)) 32.3 99.0 49.0 99.0 278 235 composition ofcomponent physical (IV) properties Morphology (1) Co-continuouscomponent No Yes No No No Yes (I) phase and component (II) phase (2)Component (II) phase Yes No Yes Yes No No forms matrix (3) Neither of(1) No No No No Yes No and (2) applies Physical Smoke generationGenerated-smoke 297 405 311 302 486 470 property properties density Dsevaluation Electrolysis Tensile strength 70 65 82 76 58 60 resultssolution-resistance retention rate (%) Chemical Salad oil- Criticalstrain 0.60 0.56 0.73 0.71 0.65 0.68 resistance resistance (%) Moldcleaning 1.47 1.41 1.70 1.66 1.33 1.38 agent-resistanceGrease-resistance 1.01 0.96 1.29 1.15 0.94 1.00 Flame retardance RankV-0 V-0 V-0 V-2 V-0 V-1 Exam- Exam- ple 14 ple 15 Resin Component (I)Parts by mass 70 70 composition Component (II) Parts by mass 30 30Component (III) Parts by mass 10 10 Component (IV) Parts by mass 15 15Component (V) Parts by mass 7 7 Total amount of vinyl % 75 75 bonding inpolymer block B of component (III) Production method step First SecondFirst Second stage stage stage stage Production method Produc- Produc-Produc- Produc- tion tion tion tion Meth- Meth- Meth- Meth- od 1 od 1 od1 od 1 Resin First raw Component (I-i) Parts by mass 70 0 70 0composition material Component (I-ii) 0 0 0 0 production feedingComponent (II-i) 10 20 0 30 method inlet Component (II-ii) 0 0 0 0Component (II-iii) 0 0 0 0 Component (III-i) 10 0 10 0 Component (III-x)0 0 0 0 Pellets prepared — 105 — 95 in first stage Second raw Component(II-i) Parts by mass 0 0 0 0 material Component (II-ii) 0 0 0 0 feedingComponent (II-iii) 0 0 0 0 inlet Component (V) 0 7 0 7 Liquid Component(IV) Parts by mass 15 0 15 0 addition pump Resin Partition ratio(IV)_((I))/(IV)_((II)) 269 312 composition of component physical (IV)properties Morphology (1) Co-continuous component No No (I) phase andcomponent (II) phase (2) Component (II) phase No No forms matrix (3)Neither of (1) Yes Yes and (2) applies Physical Smoke generationGenerated-smoke 449 449 property properties density Ds evaluationElectrolysis Tensile strength 57 54 results solution-resistanceretention rate (%) Chemical Salad oil- Tensile strength 0.60 0.54resistance resistance retention rate Mold cleaning (%) 1.31 1.25agent-resistance Grease-resistance 0.94 0.89 Flame retardance Rank V-1V-1

TABLE 2 Compar- Compar- Compar- Compar- Compar- ative ative ative ativeative Exam- Exam- Exam- Exam- Exam- ple 1 ple 2 ple 3 ple 4 ple 5 ResinComponent (I) Parts by mass 70 70 70 70 70 composition Component (II) 3030 30 30 30 Component (III) 0 10 10 10 0 Component (IV) 15 0 48 0 0Component (V) 7 7 0 12 12 Total amount of vinyl % — 75 75 75 — bondingin polymer block B of component (III) Production method — Produc-Produc- Produc- Produc- Produc- tion tion tion tion tion Meth- Meth-Meth- Meth- Meth- od 1 od 1 od 1 od 1 od 1 Resin Screw rotation speedrpm 300 300 300 300 300 composition First raw Component (I-i) Parts bymass 70 70 70 70 0 production material Component (I-ii) 0 0 0 0 70method feeding Component (II-i) 10 30 10 10 10 inlet Component (II-ii) 00 0 0 0 Component (II-iii) 0 0 0 0 0 Component (III-i) 0 10 10 10 0Component (III-x) 0 0 0 0 0 Second raw Component (II-i) Parts by mass 200 20 20 20 material Component (II-ii) 0 0 0 0 0 feeding Component(II-iii) 0 0 0 0 0 inlet Component (V) 7 7 0 12 12 Liquid Component (IV)Parts by mass 15 0 48 0 0 addition pump Resin Partition ratio(IV)_((I))/(IV)_((II)) 32.3 — 1.38 — — composition of component physical(IV) properties Morphology (1) Co-continuous component Yes No No Yes Yes(I) phase and component (II) phase (2) Component (II) phase No Yes No NoNo forms matrix (3) Neither of (1) No No Yes No No and (2) appliesPhysical Smoke generation Generated-smoke 439 477 422 1049 1362 propertyproperties density Ds evaluation Electrolysis Tensile strength 44 46 3274 68 results solution-resistance retention rate (%) Chemical Salad oil-Critical strain 0.36 0.37 0.32 0.65 0.55 resistance resistance (%) Moldcleaning 1.08 1.07 0.63 1.59 1.38 agent-resistance Grease-resistance0.66 0.66 0.39 1.05 0.94 Flame retardance Rank V-0 V-1 HB V-1 V-1Compar- Compar- Compar- Compar- Compar- ative ative ative ative ativeExam- Exam- Exam- Exam- Exam- ple 6 ple 7 ple 8 ple 9 ple 10 ResinComponent (I) Parts by mass 70 70 70 70 70 composition Component (II) 3030 30 30 30 Component (III) 10 10 10 0 10 Component (IV) 48 48 15 15 15Component (V) 0 0 7 7 7 Total amount of vinyl % 75 75 75 — 75 bonding inpolymer block B of component (III) Production method — Produc- Produc-Produc- Produc- Produc- tion tion tion tion tion Meth- Meth- Meth- Meth-Meth- od 1 od 1 od 1 od 1 od 3 Resin Screw rotation speed rpm 300 300300 300 300 composition First raw Component (I-i) Parts by mass 70 70 7070 70 production material Component (I-ii) 0 0 0 0 6 method feedingComponent (II-i) 0 0 30 10 10 inlet Component (II-ii) 10 0 0 0 0Component (II-iii) 0 10 0 0 0 Component (III-i) 10 10 10 0 10 Component(III-x) 0 0 0 10 0 Second raw Component (II-i) Parts by mass 0 0 0 20 20material Component (II-ii) 20 0 0 0 0 feeding Component (II-iii) 0 20 00 0 inlet Component (V) 0 0 7 7 7 Liquid Component (IV) Parts by mass 4848 15 15 15 addition pump Resin Partition ratio (IV)_((I))/(IV)_((II))1.22 1.04 0.61 80 9.3 composition of component physical (IV) propertiesMorphology (1) Co-continuous component No No Yes Yes Yes (I) phase andcomponent (II) phase (2) Component (II) phase No No No No No formsmatrix (3) Neither of (1) Yes Yes No No No and (2) applies PhysicalSmoke generation Generated-smoke 447 504 724 402 397 property propertiesdensity Ds evaluation Electrolysis Tensile strength 28 26 37 50 60results solution-resistance retention rate (%) Chemical Salad oil-Critical strain 0.21 0.15 0.37 0.40 0.51 resistance resistance (%) Moldcleaning 0.64 0.51 0.81 1.06 1.35 agent-resistance Grease-resistance0.19 0.17 0.44 0.72 0.89 Flame retardance Rank HB HB V-1 V-0 V-1 Compar-Compar- Compar- Compar- Compar- ative ative ative ative ative Exam-Exam- Exam- Exam- Exam- ple 11 ple 12 ple 13 ple 14 ple 15 ResinComponent (I) Parts by mass 70 70 70 70 70 composition Component (II) 3030 30 30 30 Component (III) 10 10 10 10 10 Component (IV) 15 15 15 15 15Component (V) 7 7 7 7 7 Total amount of vinyl % 75 75 75 75 75 bondingin polymer block B of component (III) Production method — Produc-Produc- Produc- Produc- Produc- tion tion tion tion tion Meth- Meth-Meth- Meth- Meth- od 4 od 3 od 4 od 5 od 7 Resin Screw rotation speedrpm 300 300 300 300 300 composition Fist raw Component (I-i) Parts bymass 70 0 0 0 0 production material Component (I-ii) 0 70 70 70 70method feeding Component (II-i) 10 0 0 0 0 inlet Component (II-ii) 0 1010 10 10 Component (II-iii) 0 0 0 0 0 Component (III-i) 10 10 10 10 10Component (III-x) 0 0 0 0 0 Second raw Component (II-i) Parts by mass 200 0 0 0 material Component (II-ii) 0 20 20 20 20 feeding Component(II-iii) 0 0 0 0 0 inlet Component (V) 7 7 7 7 7 Liquid Component (IV)Parts by mass 15 15 15 15 15 addition pump Resin Partition ratio(IV)_((I))/(IV)_((II)) 6.9 8.7 5.5 9.1 4.2 composition of componentphysical (IV) properties Morphology (1) Co-continuous component Yes YesYes Yes Yes (I) phase and component (II) phase (2) Component (II) phaseNo No No No No forms matrix (3) Neither of (1) No No No No No and (2)applies Physical Smoke generation Generated-smoke 433 410 418 433 468property properties density Ds evaluation Electrolysis Tensile strength49 52 46 53 44 results solution-resistance retention rate (%) ChemicalSalad oil- Critical strain 0.47 0.41 0.42 0.44 0.36 resistanceresistance (%) Mold cleaning 1.28 1.26 1.13 1.29 1.10 agent-resistanceGrease-resistance 0.86 0.85 0.79 0.88 0.74 Flame retardance Rank V-1 V-1V-1 V-1 V-1 Compar- Compar- Compar- ative ative ative Exam- Exam- Exam-ple 16 ple 17 ple 18 Resin Component (I) Parts by mass 70 70 70composition Component (II) 30 30 30 Component (III) 10 10 10 Component(IV) 15 15 15 Component (V) 7 7 7 Total amount of vinyl % 75 75 75 75 75bonding in polymer block B of component (III) Production method stepFirst Second First Second First Second stage stage stage stage stagestage Production method Produc- Produc- Produc- Produc- Produc- Produc-tion tion tion tion tion tion Meth- Meth- Meth- Meth- Meth- Meth- od 1od 1 od 1 od 1 od 1 od 1 Resin First raw Component (I-i) Parts by mass70 0 70 0 70 0 composition material Component (I-ii) 0 0 0 0 0 0production feeding Component (II-i) 30 0 25 5 5 25 method inletComponent (II-ii) 0 0 0 0 0 0 Component (II-iii) 0 0 0 0 0 0 Component(III-i) 10 0 10 0 10 0 Component (III-x) 0 0 0 0 0 0 Pellets prepared —110 — 105 — 85 in first stage Second raw Component (II-i) Parts by mass0 0 0 0 0 0 material Component (II-ii) 0 0 0 0 0 0 feeding Component(II-iii) 0 0 0 0 0 0 inlet Component (V) 0 7 0 7 0 7 Liquid Component(IV) Parts by mass 0 15 0 15 0 15 addition pump Resin Partition ratio(IV)_((I))/(IV)_((II)) 0.49 1.3 4.6 composition of component physical(IV) properties Morphology (1) Co-continuous component Yes Yes Yes (I)phase and component (II) phase (2) Component (II) phase No No No formsmatrix (3) Neither of (1) No No No and (2) applies Physical Smokegeneration Generated-smoke 768 709 425 property properties density Dsevaluation Electrolysis Tensile strength 32 36 42 resultssolution-resistance retention rate (%) Chemical Salad oil- Criticalstrain 0.33 0.34 0.35 resistance resistance (%) Mold cleaning 0.75 0.781.05 agent-resistance Grease-resistance 0.42 0.41 0.65 Flame retardanceRank V-1 V-1 V-0 Compar- Compar- ative ative Exam- Exam- ple 19 ple 20Resin Component (I) Parts by mass 70 70 composition Component (II) 30 30Component (III) 10 10 Component (IV) 15 15 Component (V) 7 7 Totalamount of vinyl % 75 75 bonding in polymer block B of component (III)Production method step First Second First Second stage stage stage stageProduction method Produc- Produc- Produc- Produc- tion tion tion tionMeth- Meth- Meth- Meth- od 1 od 1 od 1 od 1 Resin First raw Component(I-i) Parts by mass 70 0 70 0 composition material Component (I-ii) 0 00 0 production feeding Component (II-i) 10 20 20 10 method inletComponent (II-ii) 0 0 0 0 Component (II-iii) 0 0 0 0 Component (III-i)10 0 10 0 Component (III-x) 0 0 0 0 Pellets prepared — 90 — 100 in firststage Second raw Component (II-i) Parts by mass 0 0 0 0 materialComponent (II-ii) 0 0 0 0 feeding Component (II-iii) 0 0 0 0 inletComponent (V) 0 7 0 7 Liquid Component (IV) Parts by mass 0 15 0 15addition pump Resin Partition ratio (IV)_((I))/(IV)_((II)) 3.0 1.7composition of component physical (IV) properties Morphology (1)Co-continuous component Yes Yes (I) phase and component (II) phase (2)Component (II) phase No No forms matrix (3) Neither of (1) No No and (2)applies Physical Smoke generation Generated-smoke 492 621 propertyproperties density Ds evaluation Electrolysis Tensile strength 38 37results solution-resistance retention rate (%) Chemical Salad oil-Critical strain 0.31 0.32 resistance resistance (%) Mold cleaning 0.810.80 agent-resistance Grease-resistance 0.50 0.53 Flame retardance RankV-0 V-1

As shown in Tables 1 and 2, the resin compositions of Examples 1 to 15had excellent smoke generation properties with low generated-smokedensity during burning, and excellent chemical resistance with a hightensile strength retention rate after chemical immersion compared to theresin compositions of Comparative Examples 1 to 20.

INDUSTRIAL APPLICABILITY

According to this disclosure, it is possible to provide a resincomposition and a shaped product having excellent smoke generationproperties and chemical resistance. A shaped product containing thepresently disclosed resin composition can be suitably used forautomotive components, interior and exterior components of electricaldevices, other components, and so forth.

1. A resin composition comprising: a polyphenylene ether resin (I); apolypropylene resin (II); a hydrogenated block copolymer (I) that is anat least partially hydrogenated product of a block copolymer including apolymer block A of mainly a vinyl aromatic compound and a polymer blockB of mainly a conjugated diene compound in which a total amount of1,2-vinyl bonding and 3,4-vinyl bonding is 30% to 90%; and a phosphateester compound (IV), wherein relative to 100 parts by mass, in total, ofthe polyphenylene ether resin (I) and the polypropylene resin (II): thepolyphenylene ether resin (I) is contained in an amount of 40 parts bymass to 99 parts by mass; the polypropylene resin (II) is contained inan amount of 1 part by mass to 60 parts by mass; the hydrogenated blockcopolymer (III) is contained in an amount of 1 part by mass to 20 partsby mass; and the phosphate ester compound (IV) is contained in an amountof 5 parts by mass to 45 parts by mass, and upon dissolution of theresin composition in chloroform, a ratio (IV)_((I))/(IV)_((II)) is 10 ormore, where (IV)_((I)) represents content of the phosphate estercompound (IV) present in a fraction that dissolves in chloroform and(IV)_((II)) represents content of the phosphate ester compound (IV)present in a fraction that dissolves in o-dichlorobenzene.
 2. The resincomposition according to claim 1, wherein the ratio(IV)_((I))/(IV)_((II)) is 250 or less.
 3. The resin compositionaccording to claim 2, wherein the ratio (IV)_((I))/(IV)_((II)) is 199 orless.
 4. The resin composition according to claim 3, wherein the ratio(IV)_((I))/(IV)_((II)) is 15 to
 199. 5. The resin composition accordingto claim 1, further comprising 3 parts by mass to 15 parts by mass of atleast one phosphinate salt (V) selected from the group consisting of: aphosphinate salt represented by formula (1)

where R¹¹ and R¹² are each, independently of one another, a linear orbranched alkyl group having a carbon number of 1 to 6 and/or an arylgroup having a carbon number of 6 to 10, M¹ is at least one selectedfrom the group consisting of a calcium ion, a magnesium ion, an aluminumion, a zinc ion, a bismuth ion, a manganese ion, a sodium ion, apotassium ion, and a protonated nitrogenous base, a is an integer of 1to 3, m is an integer of 1 to 3, and a=m; and a diphosphinate saltrepresented by formula (2)

where R²¹ and R²² are each, independently of one another, a linear orbranched alkyl group having a carbon number of 1 to 6 and/or an arylgroup having a carbon number of 6 to 10, R²³ is a linear or branchedalkylene group having a carbon number of 1 to 10, an arylene grouphaving a carbon number of 6 to 10, an alkylarylene group having a carbonnumber of 6 to 10, or an arylalkylene group having a carbon number of 6to 10, M² is at least one selected from the group consisting of acalcium ion, a magnesium ion, an aluminum ion, a zinc ion, a bismuthion, a manganese ion, a sodium ion, a potassium ion, and a protonatednitrogenous base, b is an integer of 1 to 3, n is an integer of 1 to 3,j is an integer of 1 or 2, and b·j=2n.
 6. The resin compositionaccording to claim 1, wherein the total amount of 1,2-vinyl bonding and3,4-vinyl bonding in the conjugated diene compound of the polymer blockB is 65% to 90%, and the conjugated diene compound of the polymer blockB includes butadiene.
 7. The resin composition according to claim 1,wherein the phosphate ester compound (IV) includes a condensed phosphateester.
 8. The resin composition according to claim 1, wherein the resincomposition has a morphology in which a phase containing thepolyphenylene ether resin (I) and a phase containing the polypropyleneresin (II) are co-continuous or a morphology in which a phase containingthe polypropylene resin (II) is a matrix.
 9. A shaped product comprisingthe resin composition according to claim
 1. 10. The resin compositionaccording to claim 4, further comprising 3 parts by mass to 15 parts bymass of at least one phosphinate salt (V) selected from the groupconsisting of: a phosphinate salt represented by formula (1)

where R¹¹ and R¹² are each, independently of one another, a linear orbranched alkyl group having a carbon number of 1 to 6 and/or an arylgroup having a carbon number of 6 to 10, M¹ is at least one selectedfrom the group consisting of a calcium ion, a magnesium ion, an aluminumion, a zinc ion, a bismuth ion, a manganese ion, a sodium ion, apotassium ion, and a protonated nitrogenous base, a is an integer of 1to 3, m is an integer of 1 to 3, and a=m; and a diphosphinate saltrepresented by formula (2)

where R²¹ and R²² are each, independently of one another, a linear orbranched alkyl group having a carbon number of 1 to 6 and/or an arylgroup having a carbon number of 6 to 10, R²³ is a linear or branchedalkylene group having a carbon number of 1 to 10, an arylene grouphaving a carbon number of 6 to 10, an alkylarylene group having a carbonnumber of 6 to 10, or an arylalkylene group having a carbon number of 6to 10, M² is at least one selected from the group consisting of acalcium ion, a magnesium ion, an aluminum ion, a zinc ion, a bismuthion, a manganese ion, a sodium ion, a potassium ion, and a protonatednitrogenous base, b is an integer of 1 to 3, n is an integer of 1 to 3,j is an integer of 1 or 2, and b·j=2n.
 11. The resin compositionaccording to claim 4, wherein the total amount of 1,2-vinyl bonding and3,4-vinyl bonding in the conjugated diene compound of the polymer blockB is 65% to 90%, and the conjugated diene compound of the polymer blockB includes butadiene.
 12. The resin composition according to claim 5,wherein the total amount of 1,2-vinyl bonding and 3,4-vinyl bonding inthe conjugated diene compound of the polymer block B is 65% to 90%, andthe conjugated diene compound of the polymer block B includes butadiene.13. The resin composition according to claim 4, wherein the phosphateester compound (IV) includes a condensed phosphate ester.
 14. The resincomposition according to claim 5, wherein the phosphate ester compound(IV) includes a condensed phosphate ester.
 15. The resin compositionaccording to claim 6, wherein the phosphate ester compound (IV) includesa condensed phosphate ester.
 16. The resin composition according toclaim 4, wherein the resin composition has a morphology in which a phasecontaining the polyphenylene ether resin (I) and a phase containing thepolypropylene resin (II) are co-continuous or a morphology in which aphase containing the polypropylene resin (II) is a matrix.
 17. The resincomposition according to claim 5, wherein the resin composition has amorphology in which a phase containing the polyphenylene ether resin (I)and a phase containing the polypropylene resin (II) are co-continuous ora morphology in which a phase containing the polypropylene resin (II) isa matrix.
 18. The resin composition according to claim 6, wherein theresin composition has a morphology in which a phase containing thepolyphenylene ether resin (I) and a phase containing the polypropyleneresin (II) are co-continuous or a morphology in which a phase containingthe polypropylene resin (II) is a matrix.
 19. The resin compositionaccording to claim 7, wherein the resin composition has a morphology inwhich a phase containing the polyphenylene ether resin (I) and a phasecontaining the polypropylene resin (II) are co-continuous or amorphology in which a phase containing the polypropylene resin (II) is amatrix.
 20. A shaped product comprising the resin composition accordingto claim 8.